Compounded lubricant



Patented Aug. 13, 1946 I accuses I cooonnpn LUBRICANT Dilworth'l. Rogers, Plainfleld, N. 3., assignor to Standard Oil Development Company, a oorporation o! Delaware No Application ch Serial No. 528,953

'12 Claims. (c1. 252-3211) I 1 v This invention relates to relates more'particularly to a new type oi additive for improving the are further reactedwith a combination of the ole oia mixture of elemental phosphorus and elemental sulfur or, more preferably, a phosphorus sulfide, the resulting products have properties the phosphorus and sulfur, particularly with re gard to their efiectiveness as blending agent for .,mineral lubricating oils, since they are distinctly superior in the property of reducing the corrosion of alloy bearings and in promoting engine clean liness. These products are described fully and claimed in my 'co-pending application of even c lng date. It has further been found that salts or such products, obtained by reacting the prodnets with a metal, a metallic base or an organic base, or in any other manner, are equally valu= able.'especially as corrosion inhibitors, extreme pressure agents and anti oxidants and as agents for promoting engine cleanliness, and in some a method of prevent ing the deterioration of organic materials, and it properties of mineral lubriconversion of the resulting product to a salt, as

by reactionwith a metallic base. As pointed out Y in application Serial Number 457,1, cheer the functions of the aromatic material is to stabilize eating oils. the sulfur present in the reaction product of the In co-pending application Serial No. 457,146, sulfur halidewith the unsaturated compound. filed September 3,1942, the same being a joint Although all or a greater part oi'the halogen application of Carl Winning and the present appresentlis removed by the second reaction as hinplicant, there were described additives for lubri .drosen halide, thearomatic compound does not eating oils which were. prepared by reacting an m act-solely as a dehydrohalogenatingagent, since unsaturated compound, such as ,diisobutylena an pp c le Proportion of the same actually with a sulfur halide and further reacting the enters into the reaction and becomes a constituproduct thus'tormed with an aromatic compound, ent of the reaction product, The resulting matee. a. phenol. These products were shown to have rial is a. mixture of compounds some of which the property of notably reducing the corrosion of. ware believed to possess an aromatic ring struc copper-lead and similar bearings when blended ture with a side chain containing sulfur in a stainto lubricating oils, and of notably improving bilizecl form. Althou h h Struct re of he engine cleanliness and reducing ring sticking, pigmaterials obtained in the third step is not defiton' skirt varnish formation and the sludging ni ly nown, the products d n amwm in fi tendencies of oils used in automotive engines. 20 h sbhoruswhich enhances their desirable P Theproducts were also found to be useful as cities. and it is believed that organo-substituted general anti-oxidants fororganic materials. h ids of phosphorus re present. Itis n It has'now been found, in accordance with the intended that the invention be limited by any present invention, that when products of the type theory s to the exact nature of the chemical described in application Serial Number 457,146 25 reactions that t place was o ny art ul chemical structure of the intermediate or final merits. phosphorus and sulfur, either in the form products.

. In the first reaction of the process any sulfur halide may be reacted with a compound containto lug one or more unsaturated carbon-to-carbon which are notably superior to those shown to be possessed by the products before reacting with i linkage, e. g., a 0:6 group or a CEC- group which forms apart of a non-hcnzenoid organic group. -Bythe term non-benzenoid'is meant any organic group other than a ring structure having the typical benzene-like linkage found in benzene and its homologs and in condensed structures such as those of naphthalene, anthra/cene,

and the like. 'The desired reactive unsaturated linkages may be found in'many types of groups ing, such as in eleflns. in olefinic side chains of aromatic compounds, in cycle-oleflns, in terrenes, in hetercyclic compcunds, etc. Thus, ylene,

1 isobutylene, diisobutylene, triisobutyleue, the co cases distinctly superior; and these salts, their preparation and uses form the subject matter of thepresent application. I

'The preparation of the new additives of the 4 present invention thus involves Your fundamental steps: (1) the reaction of an unsaturated organic compound with a sulfur halide; (2) a further reaction with an aromatic compound: (3) a further reaction with phosphorus and sulfur; and (4) dimer of isobutylene and normal butene, cracked gasoline fractions, cracked paramn wax,'medium or high molecular weight polybutene or. other viscous olefin mlymers, cyclopentene, cyclohcxene, butadiene, pentadiene, isoprene, styren .3, oleic acid, oleyl alcohol, pine oil; terpcnes and similar unsaturated materials may be used. Oiefins of less than four carbon atoms are in general not considered particularly suitable for the present invention, although This not intended that their use be excluded. Derivatives of the above described compoundscontainlng various substitueut since the substituent groups normally do not interfere with the principal reaction.

The most suitable sulfur halides are sulfur dichloride and monochloride, especially the monochloride. The olefinic material and sulfur halide related compounds are phenol itself and its alkylated derivatives, such as the cresols, xylenols,

' mesitol, butyl phenol, tert.amyl phenol, di-tert.-

may be reacted in any desired proportions, but the more preferred ratio of olefinic material to sulfur halide is within the range from about 3:1 to 1:1 (molal ratio). Higher ratios may often be used when a portion of the olefinic material is to serve as a solvent to be removed later as unreacted material. The temperatures which have been found most satisfactory for this reaction are from about 20 to about 50 C. (about 70-125 F), but the method may be carried out at considerably higher or lower temperatures if desired. Catalysts are not required.

In the second reaction of the process, in which the reaction product of the sulfur halide with an olefin or like material is further reacted with an aromatic compound, the ratio of about one part by weight of aromatic materialto one-half to ten parts by weight ofsulfur halide-olefin reactionproduct may be used. When the aromatic material is a phenol, the most preferred ratio is about one part by weight of the phenol to three to ten parts by weight of the sulfur halide-olefin reaction product. a In reacting phenol itself with the diisobutylene-sulfur monochloride condensate the most desirable ratio is about one part of phenol to eight to ten parts of the condensate. The temperature of the reaction may range from aboutfi to about 160 C. (about 100-320 F.) but the most desirable range has been found to be between about 80 and about 140 C. (about 175-285" F.). In general, solvents are not required in either the first or second steps of the process because of the nature of the reactants employed; For example, when diisobutylene is used as the olefin source, any excess of this which .is present undoubtedly acts in a solvent capacity. Where an olefinic material of higher molecular weight is used or where the reaction mixture is not sufficiently' fluid the reaction may be aided by the use of an organic solvent such as a chlorinated hydrocarbon or the like. Also, with some types of reactants the presence of water, an alcohol or an ether will be found to'be beneficial.

The aromatic materials which may be used in the process include all types. The aromatic hydrocarbons, such as benzene, naphthalene, amyl benzene, wax alkylated naphthalene, and the like, may be used, although compounds containing substituent groups, such as phenols, aniline, salicylic acid, substituted salicylic acids, alpha naphthol, diphenyl oxide, etc., are more readily reacted. In such substituted compounds, how ever, there must always be present in the arcmatic nucleus at' least one replaceable hydrogen atom. When unsubstituted hydrocarbons, particularly those having no alkyl groups, are sin-- tached to the aromatic nucleus.

amyl phenol, tertiary octyl phenol, cetyl phenol, cashew nut shell phenol (cardanol), wax alkylated phenols, phenyl phenol, petroleum phenols and the like, as well as the naphthols. Derivatives of such phenols containing substituents, such as halogen, nitro groups, amino groups, keto groups, carboxyl groups, ester groups, aroxy groups, etc, may also be used, as well as the corresponding thiophenols and compounds having more .than one hydroxyl or mercaptan group at- Likewise metal salts of the phenolic compounds may be employed.

It may be mentioned that the chlorophenols and chlorinated aromatic hydrocarbons are particularly valuable in forming compounds useful in extreme pressure lubricants.

Another particularly preferred class of aro matic compounds are the arylamines, such as aniline, diphenyl amine, phenylene-diamine, aminophenols and the like. These are particularly useful because of the additional antioxidant properties of the attached amino groups.

Aromatic compounds containing other substituent groups are also contemplated for use in accordance with thi invention. These include compounds containing aryl, nitro, nitroso, nitrile, thiocyanate, aldehyde, carboxyl and ether groups, as well as groups containing sulfur which partially or wholly replaces the oxygen of these groups. Included also are compounds in which a'metal is present, as in a metal carboxylate group, an organo-metallic group, a metal alcoholate group, or the like.

Another particularly preferred class of aromatic compounds which may be reacted with the sulfur halide-olefinic reaction products to produce unusually valuable addition agents are the aromatic sulfides, particularly the phenol sulfides in which two groups are combined with one or more sulfur atoms. The phenol sulfides are conveniently prepared by reacting phenols and alkylated phenols with sulfur halides. Such materials are known to be useful in' themselves as anti-corrosion agents, and their usefulness is increased by reacting them or their metal salts with the sulfur halide product of the present invention to form products containing additional sulployed, a condensing agent, such as aluminum fur in stabilized form and further reacting these products with a phosphorus sulfide.

If desired, the products after the reaction with the aromatic compound as described above may be further treated before reacting with a phosphorus sulfide or with phosphorus and sulfur. For example, those obtained by reaction with phenols or with phenol sulfides may be converted to metal salts, such as those of tin, barium, calcium, magnesium, zinc, nickel or aluminum, and the metal derivatives thus formed further reacted with a phosphorus sulfide. Likewise, any free phenolic groups prcsent may be converted to ester or ether groups.

In the third basic step of the process the products of the foregoing reactions are further reacted with the elements'phosphorus and sulfur. This may be accomplished by adding a mixture of the substances in elementary form to the heated reaction products, or byadding a sulfide of phosphorus, such as P283, PzSs, P4S3, P487, eta, or-the like, or by treating with amixture of sulfur and/or phosphorus and a sulfide of phosphorus. or by treating with any other substance or substances containing essentially only the elements phosphorus and sulfur, or phosphorus and sulfur in combination with elements-which do not interfere with the reaction and which are not harmful to the final product. When elementary phosphorus is used it may be either in the white (yellow) or red allotropic form, and sulfur may likewise be used in any of its allotropic forms.

However, it is ordinarily more convenient to use a sulfide of phosphorus in carrying out the reaction. The proportions of phosphorus sulfide to the sulfur halideolefin aromatic condensate may vary over a considerable range. In general, about 5% to about 25% and preferably about 8% to about of phosphorus sulfide may be used, based on the weight of the product from the previous condensation of aromatic material with the sulfur halide-olefine product.

Although the reaction can be brought about by fusing the phosphorus and sulfur or phos phorus sulfide with the above described reaction productjit ismore convenient to carry out. the reaction with the aid of solvents, particularly petroleum hydrocarbon solvents, or by the use of an excess of the olefinic reaction product when the entire series of reactions take placein one reaction vessel. Chlorinated or aromatic solvents may also be used. In'the reaction with sulfides of phosphorus, temperatures in the range of 60 to 200 C. may be employed, but temperatures of 90 to 150 C. are preferred.

If desired, the reaction with'thesulfideof phosphorus may be conducted in a lubricating oil medium. For example, a 50% concentrate of the olefin-sulfur halide-aromatic condensate may be prepared in lubricating oil as described in Example 1 of the aforementioned co-pending application Serial Number 457,146, and then treated with the sulfide of phosphorus and finally filtered.

Ingen'eral', the preferred method of carrying out the first three basic steps of the presentinvention is first to treat the olefin or other unsaturated material with the sulfur halide, then react with the aromatic material, and finally add the phosphorus and sulfur or phosphorus sulfide. However, variations of this procedure may be employed, as by adding the sulfur halide to a mixture of the olefin and aromatic material, provided the olefin and aromatic material do not react directly with each other, and then further reacting with the phosphorus sulfide. It is to be understood that any of the products disclosed in or prepared by the methods de scribed in application Serial Number 451ml; 1119;. be further reacted with a combination of phosphorus and sulfur to form a product which may be converted to a salt additive of the present invention.

Products which, in the form of their salts, are especially adapted for use in extreme pressure lubricants may be prepared by halogenating the phosphorus sulfide reaction products; or, the halogen may be introduced by using compounds containing phosphorus, sulfur andhalogen, e. g., PSC13, PSBrg, PSBrClz, PzS'zBm, and the like, in place of or in addition to the phosphorus sulfide in the third step of the preparation.

The fourth and final basic step of the process, i. e., the conversion of the product of the first three steps into a salt, is generally accomplished simply'by reacting the product with a metal, metal oxide, metal hydroxide, or other suitable metal compounds, or with a suitable non-metallic 5 base. This may be done by heating the reactants in the presence of a suitable'solvent, such as an alcohol or lubricating oil. It is insome cases possible and desirable to conduct the third and fourth steps of the process simultaneously, e.

by reacting the olefin-sulfur halide-aromatic condensate with a mixture of a phosphorus sulfide" and a metallic oxide. The salts which r. em ployed in accordance with the present; invention include salts of all types, i. e., metal-salts as well as salts of non-metallic bases, such as onium salts of all types, including ammoniun'i, alliylammonium, quaternary" ammonium, sulionium and phosphonium salts, as well as amine salts and salts of organic bases generally. The most preferred metallic salts are the salts of metals of group II, particularly the salts of caliciun, barium, magnesium and zinc, also the alkali metal salts and salts of tin and aluminum. It has been found to be somewhat preferable to react an amount of metal or base with the phosphorus sulfide treated product which is at least equivalent to one atom of a monovalent metal for each atom of phosphorus present.

As noted above, the additives oi the present invention are particularly useful for reducing ing in engine operation.

corrosiveness of oils toward alloy bearings and. for improving engine cleanliness as indicated by the reduced quantities of deposits found in ring grooves, on piston skirts and in other parts of the engine in which lubricants compounded with the additives are used.

.Another noteworthy advantage of the additives prepared in accordance with the present inven tion is their ability to reduce exhaust valve stick- In certain tspes of service, such as in railway Diesel engines, oils of otherwise satisfactory characteristics are often objectionable because of their tendency to cause sticking or erratic action of the exhaust valves, presur'nabl; through the building up of oil position products on the hot portions'of the valve stems. Additives of the present invention markedly retard this tendency in oils in which they are blended. Since fuel combustion products also come into contact with the valve parts. the additives may likewise be added to the fuels for both Diesel and gasoline engines to prevent or minimize the sticking of valves.

Generally, the additives or" the present invention are most advantageously blended with lubri eating oil base stocks in concentrations between the approximate limits of 9.02% and 5.0%, and preferably from 0.1% to 2.0%, although larger amounts may be employed. The exact amount to be used depends to a certain extent on the particular compounds used, the character of the mineral oil base and the operating conditions of the engine in which the lubricant is' to he employed. When the additives are to be used extreme pressure lubricants, concentration of l to 15% are desirable and concentrations of 2 to 10% are preferred.

Concentrates of the additives in oil may also be prepared in, say, 25% to. 75% concentration of additiveand the concentrate later'blended with other oilsto give a final blend of lubricating oil containing the desired precentage of additive. Such concentrates are often desirable, to save shipping weight and space and to facilitate blending operations.

Examples of the'preparation and utilization of useful products in accordance v"?! the method of the present invention will be des ed n exampleswhich follow, but it is to be under that these example; do not limit the scope of the invention in any way.

Example 1 1233 grams of diisobutylene was placed in a reaction fiask equipped with a heater, stirrer and reflux condenser. Then, over a period of three to four-hours, 472 grams of S201: was added with stirring, the reaction temperature being kept at 40-45 C. After stirring for an additional period of approximately an hour 94 grams of phenol was added rapidly, the temperature raised to 100 0., and the stirring continued for an additional period of about two hours. 71 grams ofPzsa was then added over a 15 minut period while the temperature was maintained at 100 0. Heating was continued with stirring at 100-105 C. for an additional period of about two hours. The product was allowed to cool to room temperature 1 and then filtered through Hy-fio, leaving a-very slightresidue. The filtrate was divided into two parts (850 cc. each) and one portion was steam distilled at 100 0., yielding 282 grams of colorless, water-insoluble distillate. The distillation residue was separated from the water presentand then dried in a stream of nitrogen for an hour at 105 C. The final product had the following analysis:

Percent 26.94

To 300 grams of the product prepared as described above 10 grams of zinc oxide was added and the mixture heated to 80 0. Then 250 cc.

of isopropyl alcohol was added and heating was continued for two hours at 100 C, while a stream of nitrogen was blown through the mixture. The material, which had become free of the alcohol by heating,- was then filtered through Hy-flo, giving as a. final product a light-colored, viseo liquid soluble in lubricating oil.

Example 2 The efiectiveness of the product prepared as described in Example 1 in inhibiting the corrosion of a typical lubricating oil toward the.

surfaces of copper-lead bearings was determined by a test which will be described below. The

various blended oils may be employed as well the bearings used in a given test at the end of the various four-hour periods are given in the table. I

I Table Cumulative bearing weight loss (mg.

. per25sq.cm.aurtace) Oil 4 8 12 16 20 24 28 32 86 hrs. hrs. hrs. hrs. hrs. hrs. hrs. hrs. hrs.

BaseoiL- 5' 181 Base oil 1% product of Exampei 0 0 0 0 0 0 0 10 29 The products of the present invention may be employed not only in ordinary hydrocarbon lubricating oils but also in the "heavy duty" type of lubricating oils which have been compounded with such detergent type additives as metal soaps, metal petroleum suli'onates, metal phenates, metal alcoholates, metal phenol sulfonates. metal alkyl phenol sulfides, metal organo phosphates, thiophosphates, phosphites and thiophosphites, metal salicylates, metal xanthates and thioxanthates, metal thiccanbamates, reaction products of metal phenates and sulfur, reaction products of metal phenatesand phosphorus sulfides, and the like. Thus the new additives of this invention may be used in lubricating oils containing such addition agents as barium tern-cetyl phenol sulfides, calcium tertamyl phenol sulfide, nickel oleate, barium octa' decylate, calcium phenyl stearate, zinc diisopropyl salicylate, aluminum naphthenate, calcium cetyl phosphate, barium di-tert.-amyl phenol sulfide, calcium petroleum sulfonate,

zinc methyl cyclohexyl thiophosphate, calcium dichlorostearate, etc.

The lubricating 011 base stocks of this invention may be straight mineral lubricating oils, or distillates derived from parafflnlc, naphthenic, asphaltic 'or mixed base crudes, or, if desired,

as residuals, particularly those from which asphaltic. constituents have been carefully removed.

, The oils may be refined by conventional methods base oil used was a refined mineral lubricating:

oil of SAE 20 grade. A blank sample of, this oil as well as a sample of the oil. to which 1% of the additive was added were submitted to the following corrosion test: V

500 cc. of the oil were placed in a glass oxidation tube (13" long and 2%! diameter) fitted at the bottom with a /4" bore air inlet tube perforated to facilitate air distribution. The oxidation tube was then immersed in a heating bath so that the oil temperature was maintained at 325 F. during the test. Two'quarter sections of automotive bearings of copper-lead alloy of known weight having a total area of sq. cm.

using acid. alkali and/or clay or other agents such as aluminum chloride, or they may be extracted' oils produced, for example, by solvent extractionwith solvents of the type of phenol,

sulfur dioxide, furfural, dichloro ethyl ether, propane, nitrobenzene, crotonaldehyde,"'etc. Hy-

drogenated oils or white oils may be employed as well as synthetic oils prepared. for example,

by the'polymerization oi oleiins or by the reaction of oxides of carbon with hydrogen or by the hydrogenation of coal or it products. In certain instances cracking coal tarfractions and coal tar or shale oil 'distillates may also be used. Also, for special'applications, animal, vegetable or-fish oils or their hydrogenated or voltolized products may beemployed, either alone or in admixture with mineral oils.

For the best results the base stock chosen should normally be that oil which without the new additives present gives the optimum performance in the service contemplated. However, since oneadvantage of the additives is that their use also makes feasible the employment or less satisfactory mineral oils or other oils, no strict rule can be laid down for the choice of the base stock. Certain essentials must of course-m observed. The oil must possess the viscosity and volatility characteristics known to be required for the soaps, sludge dlspersers,

' as naphthenic alcohols;

, alcohol,

compositions, and greases.

seryice contemplated. The oil must be a satisfactory solvent for the additive, although in some cases auxiliary solvent agents may be used. The

lubricating oils, however they may have been produced, may vary considerably in viscosity and other properties depending upon he particular use for which they are desired, but they, usually range from about 40 to 150 seconds Saybolt viscosity at 210 F. For the lubrication ofcertain low and medium speed Diesel engines the general practice has often been to use a lubricating oil base stock prepared from naphthenic or aromatic crudes and having a Saybolt viscosity at 210 F. of 45 to 90 seconds and a viscosity index of to 50. However, in certain types of Diesel service, particularly with high speed Diesel engines, and iii-gasoline engine service, oils of higher viscosity index are often required, for example up to 75 or 100, or even higher, viscosity index.

' In additionto the materials to be added according to the present invention, other agents may also be. used such as dyes, pour depressors, heat thickened fatty oils, sulfurized fatty oils, organo metallic compounds, metallic or other antioxidants, thickeners, viscosity index improvers, oiliness agents, defoaming or antifoaming agents, resins, rubber, olefin polymers, voltolized fats, voltolized mineral oils, and/or voltolized nation of-theelements sulfur and.

with a product'obtainecl by reacting phenol with sulfur chloride derivative of an olefin.

, 2. A lubricant comprising a mineral lubricating oil base stock and a small proportion, sufiicient to stabilize the said oil against deterioration, of a metal salt of a reaction product of a combi phosphorus with a product obtained by reacting phenol with a sulfur monochloride derivative of diisobutylene.

waxes and colloidal solids such as graphite or zinc oxide, 'etc. Solvents and assisting agents, such as esters, k'etones, alcohols, I

aldehydes, halogenated 0r nitrated compounds, and the like, may also be employed.

Assisting agents which are particularly desirable are the higher alcohols having eight or more carbon atoms and preferably 12 to 20 carbon atoms. The alcohols may be saturated straight and branched chain aliphatic alcoholssuch as octyl alcohol, CsHrzOH, lauryl alcohol, ClilHiibOH, cetyl alcohol, CrcHaaOH, stearyl alcohol, somea metal salt of oil base stock and about 0.1%

3. A lubricant comprising a minerallubricating to about 2.0%by weight of a metal salt of a reaction product of a combination of the elements sulfur and phosphorus with a product obtained by reactingabout one part by 'weightof to ten parts by weight of a sulfur monochloride derivative of diisobutylene.

4. A lubricant comprising a mineral lubricating oil base stock and asmali proportion, sumcient to stabilize the ,said oil against deterioration, of

a reaction product of a'phosphorus sulfidewith a product obtained by reacting a phenol with a sulfur chloride derivative of an olefin;

times referred to as octadecyl alcohol, CmHa'rOI-I,

and the like; the corresponding olefinic alcohols such as oleyl alcohol;

and aryl substituted for instance, phenyl or octadecyl benzyl alcohol or mixthese various alcohols, which may be alkyl alcohols,

tures of pure 'or substantially pure synthetic alcohols. One may also use mixed naturally occurring alcohols such as those found in wool fat (which is known to contain a substantial percentage of alcohols having about 16 to 18 carbon atoms) and in sperm oil (which contains a high percentage of cetyl alcohol); and although it is preferable to isolate the alcohols from those materials, for some purposes, the wool fat, sperm oil or other natural products rich in alcohols may be used per se.

Products prepared synthetically by chemical processes mayalso be used, such as alcohols prepared by the oxidation of petroleum hydrocarbons, e. g., parafiin wax, petrolatum, etc.

vIn addition to being employed in crankcase octyl 1 cyclic alcohols, such' the metal of the salt oil base stock and a product obtained to stabilize the a metal saltfof 5. A lubricant comprising a mineral lubricatingoil base stock and a small proportion, sufiicient said-oil against deterioration, of a reaction product of a phosphorus sulfide with'a product obtained by reacting phenol with a sulfur .monochloride derivative of diisobutylene.

6. A composition according to claim 5 in which is a metal of group II of the periodic table.

'7. A lubricant comprising a mineral lubricating by reacting about 1 to about rtions of an olefin with 1 moof a sulfur halide, further reabout 10 parts by weight of 3 molecular propo lecular proportion acting about -3' to the product thus formed with 1 part by weight of a phenol, further formed with about 5% to' about 25% of its weight of a phosphorus sulfide, and finally converting lubricants and in extreme pressure lubricants, the

additives or the present invention may also be used in spindle oils, textile oils, metal cutting oils, engine flushing oils, turbine oils, insulating and transformer oils, steam cylinder oils, slushing Also their use ,in motor fuels, Diesel fuels and kerosene is contemplated. Since these additives exhibit antioil base stock and oxidant properties andare believed also to possess -ability to modify surface activity, they may be employed in asphalts, road oils, waxes, fatty oils of animal or vegetable origin, soaps, and plastics,

Similarly, they may be used in natural and it the product thus formed into a metal salt of the same by reaction with a' metal-containing substance, the amount of metal so reacted being at least equivalent, on a valence basis, to 1 atom of a monovalent metal for each atom of phosphorus introduced by means of the said phosphorus sulfide. I

-8. A lubricant comprising a mineral lubricating a small proportion, sumcient to stabilize the oil against deterioration, of a metal salt of'a reaction product of phosphorus pentasulflde with a product obtained by reacting a phenol with a sulfur chloride derivative of an olefin, the metal of the salt being a metal of group II of the periodic table.

9. A lubricant comprising a mineral lubricatingsolely by the terms, of the phenol with about eight about 0.02% to about 5% of reacting the product thus' 1 derivative of anolefln.

' 12 of a phosphorus sulfide with a product obtained by reacting a phenol with a sulfur halide derivative of a compound containing an olefinic linkage. e

12. An extreme pressure lubricant comprising a mineral lubricating oil base stock and about 2 to about-10% or a metal salt of a reaction product of a phosphorus sulfide with a product obtained by reacting a chlorophenol with a sulfur halide Dniwort'm 'r.- ROGERS. 

